Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
  • C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
  • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
  • B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
  • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
  • B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
  • B60R13/0212—Roof or head liners
  • B60R13/0225—Roof or head liners self supporting head liners
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
  • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
  • B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
  • B60R13/0237—Side or rear panels
  • B60R13/025—Pillars; Roof rails
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0025—Foam properties rigid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0041—Foam properties having specified density
  • C08G2110/005—< 50kg/m3
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

• the present invention relates to predominantly open-cell, cold-formable, compressed rigid polyurethane foams, to a process for their production and to their use for the manufacture of soft trim for cars, especially inside roof linings, roof stiffening boards and column trim.
• PUR foams as an intermediate layer of sandwich structures, and their use for the manufacture of soft trim for cars, are known.
• Sandwich boards for use as inside roof linings, roof stiffening or column trim are usually manufactured by the cold-forming process in which the rigid PUR foam board is provided on both sides with a thermosetting adhesive and reinforcing materials, such as glass fiber and/or natural fiber mats or non-woven fabrics and/or glass fiber rovings, as well as facings made of paper, thermoplastic sheets and/or non-woven fabrics and optionally decorative layers, to form a sandwich which is compressed in a mold at temperatures of 100 to 150° C.
• a thermosetting adhesive and reinforcing materials such as glass fiber and/or natural fiber mats or non-woven fabrics and/or glass fiber rovings, as well as facings made of paper, thermoplastic sheets and/or non-woven fabrics and optionally decorative layers
• thermo-formable rigid PUR foams for the manufacture of soft trim for motor vehicles is described, e.g., in Kunststoff-Handbuch, Polyurethane, Volume VII, Carl Hanser Verlag, Kunststoff, Vienna, 2nd edition, 1983, pp 318-319.
• thermo-formable, heat-crosslinkable rigid PUR foams are produced by reacting polyisocyanates with polyol components on a double conveyor belt.
• ⁇ -Caprolactam and/or nonylphenol are used as compounds for blocking NCO groups so that, during thermo-forming, the foam is transformed from a rather thermoplastic material to a thermosetting material by means of a second reaction.
• EP-A 0 437 787 describes a discontinuous process for the production of open-cell, cold-formable rigid PUR foams with densities of 25-30 kg/m 3 by reaction of mixtures of diphenylmethane diisocyanates (MDI) and polyphenylpolymethylene polyisocyanates, having an MDI content of 70 to 90 wt. %, with a component composed of 50 to 70 wt. % of a difunctional and/or trifunctional polyoxyalkylene polyol having a hydroxyl number of 28 to 600, 20 to 35 wt. % of a difunctional phthalic acid polyester having a hydroxyl number of 150 to 440, 2 to 10 wt.
• MDI diphenylmethane diisocyanates
• polyphenylpolymethylene polyisocyanates having an MDI content of 70 to 90 wt. %, with a component composed of 50 to 70 wt. % of a difunctional and/or trifunctional polyoxy
• glycerol 3.5 to 7 wt. % of water, 0.3 to 1 wt. % of an incorporatable tertiary amine catalyst and 0.1 to 2 wt. % of a silicone foam stabilizer.
• thermoplastically formable rigid PUR foams can be produced by reaction of mixtures of diphenylmethane diisocyanates (MDI) and polyphenylpolymethylene polyisocyanates with mixtures of polyhydroxyl compounds which contain 40 to 60 wt. % of a trifunctional polyoxyalkylene polyol having a hydroxyl number of 350 to 500, 15 to 30 wt. % of a difunctional polyoxyalkylene polyol having a hydroxyl number of 200 to 350, 5 to 20 wt. % of a difunctional to trifunctional polyoxyalkylene polyol having a hydroxyl number of 25 to 40 and 15 to 30 wt.
• MDI diphenylmethane diisocyanates
• polyphenylpolymethylene polyisocyanates polyhydroxyl compounds which contain 40 to 60 wt. % of a trifunctional polyoxyalkylene polyol having a hydroxyl number of 350 to 500, 15 to 30 wt. % of a
• the foam blocks produced continuously or batchwise, have densities of 18 to 45 kg/m 3 .
• Disadvantages of the process for the production of foam sheets from rigid PUR foam blocks include the expense of cutting or sawing and the resulting waste from the top end, bottom and edge regions of the blocks.
• the object of the present invention is to provide a method for continuously producing, on a double conveyor belt, predominantly open-cell rigid PUR foam boards capable of being compressed by the cold-forming process to make soft trim for cars.
• the present invention is directed to predominantly open-cell, cold-formable, compressed rigid polyurethane (PUR) foams obtainable by reacting
• the rigid PUR foams of the present invention are preferably produced by the double conveyor belt process. They are preferably used for the manufacture of soft trim for cars, especially inside roof linings, roof stiffening boards and column trim.
• the invention is also directed to a continuous process for the production of cold-formable, compressed, open-cell rigid polyurethane foams by the double conveyor belt process, wherein
• Component A) used in this process must include an organic polyisocyanate component a) made up of
• Component B) used in this process is an isocyanate-reactive component which must include polyhydroxyl compounds b) which include
• Additional materials which are preferably included in component B) include:
• the catalysts d) include any of the compounds that accelerate the reaction of the reactants containing reactive hydrogen atoms, especially hydroxyl groups, and the water with the organic polyisocyanates.
• Suitable catalysts are metal-organic compounds, preferably organic tin compounds such as tin(II) salts of organic carboxylic acids, for example tin(II) acetate, tin(II) octanoate, tin(II) ethylhexanoate and tin(II) laurate; the dialkyltin(IV) salts of organic carboxylic acids, for example dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate; tertiary amines such as triethylamine, tributylamine, dimethylcyclohexylamine, dimethylbenzylamine, N-methylimidazole, N-
• Suitable catalysts are tris(dialkylamino)-s-hexahydrotriazines, especially tris(N,N-dimethylamino)-s-hexahydrotriazine; tetraalkylammonium salts, for example N,N,N-trimethyl-N-(2-hydroxypropyl)formate, and N,N,N-trimethyl-N-(2-hydroxypropyl)2-ethylhexanoate; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; alkali metal hydroxides such as sodium hydroxide; alkali metal alcoholates such as sodium methylate and potassium isopropylate; and alkali metal or alkaline earth metal salts of fatty acids having 1 to 20 C atoms and optionally lateral OH groups.
• tetraalkylammonium salts for example N,N,N-trimethyl-N-(2-hydroxypropyl)formate, and
• isocyanate-reactive tertiary amines such as N,N-dimethylaminopropylamine, bis(dimethylaminopropyl)amine, N,N-dimethylaminopropyl-N′-methylethanolamine, dimethylaminoethoxyethanol, bis(dimethylaminopropyl)amino-2-propanol, N,N-dimethylaminopropyldipropanolamine, N,N,N′-trimethyl-N′-hydroxyethylbisaminoethyl ether, N,N-dimethylaminopropylurea, N-(2-hydroxypropyl)imidazole, N-(2-hydroxyethyl)imidazole and N-(2-aminopropyl)imidazole, and/or the reaction products of ethyl acetoacetate, polyether polyols and 1-(dimethylamino)-3-amin
• the polyisocyanate component used in the practice of the present invention includes mixtures of 4,4′-, 2,4′- and 2,2′-diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates (crude MDI).
• Crude MDI polyphenylpolymethylene polyisocyanates
• the component b1) may be any of the known difunctional and/or trifunctional polyoxyalkylenepolyols having a hydroxyl number ranging from 25 to 40, preferably, those obtained by reacting ethylene oxide and/or propylene oxide with one or more trihydric polyols such as glycerol or trimethylolpropane.
• the component b2) may be any of the known trifunctional and/or tetrafunctional polyoxyalkylenepolyols having a hydroxyl number ranging from 400 to 650, preferably, those obtained by reacting ethylene oxide and/or propylene oxide with one or more polyols or amines such as glycerol, trimethylolpropane, triethanolamine, ethylenediamine, ortho-toluenediamine, mixtures of sugar and/or sorbitol with glycols, etc.
• polyols or amines such as glycerol, trimethylolpropane, triethanolamine, ethylenediamine, ortho-toluenediamine, mixtures of sugar and/or sorbitol with glycols, etc.
• the component b3) may be any of the known difunctional polyoxyalkylene polyols having a hydroxyl number ranging from 150 to 550, preferably those obtained by reacting ethylene oxide and/or propylene oxide with one or more glycols such as ethylene glycol, diethylene glycol, 1,2- or 1,3-propylene glycol, 1,4-butanediol, etc.
• the component b4) may be any of the known difunctional polyesters having a hydroxyl number ranging from 200 to 350, preferably, those prepared by esterifying phthalic anhydride and/or adipic acid with ethylene glycol, diethylene glycol, propylene glycol, etc. It is particularly preferred to use a polyester obtained from phthalic anhydride, diethylene glycol and ethylene oxide.
• the component e) is preferably from 0.5 to 2 wt. % of any of the known silicone foam stabilizers.
• foam stabilizers e) are siloxane/polyoxyalkylene copolymers, organopolysiloxanes, ethoxylated fatty alcohols and alkylphenols, and ricinoleic acid esters.
• Effective cell openers f) are, e.g., paraffins, polybutadienes, fatty alcohols and dimethylpolysiloxanes.
• auxiliary substances and additives g) that can optionally be used in the practice of the present invention are emulsifiers, reaction retarders, ageing and weathering stabilizers, plasticizers, inorganic flame retardants, phosphorus-containing and/or halogen-containing organic flameproofing agents, substances with a fungistatic and/or bacteriostatic action, pigments and dyes, and the conventional organic and inorganic fillers.
• emulsifiers which may be mentioned are ethoxylated alkylphenols, alkali metal salts of fatty acids, alkali metal salts of sulfated fatty acids, alkali metal salts of sulfonic acids and salts of fatty acids and amines.
• the foams of the present invention are produced using double conveyor belt technology. It has proven to be advantageous to operate by the two-component process and to combine the components b)-g) into a processing component (B) and react this with the organic polyisocyanates a) as a processing component (A).
• the processing components (A) and (B) are mixed in a mixer at temperatures of 15 to 40° C., preferably of 20 to 35° C., in a ratio corresponding to an index of 95 to 125, preferably of 100 to 120.
• a low-pressure mixing head for example, can be used as the mixer.
• the mixture of (A) and (B) is introduced continuously between two facings, for example, by means of an oscillating mixing head, so as to foam up between the conveyor belts heated to 40-90° C. After the foam has formed on the conveyor belts and the foam has cooled, optionally, one or both facings are removed and the foam produced is optionally cut.
• the compressed rigid PUR foams produced by the process according to the invention have a density of 20 to 50 kg/m 3 , preferably of 25 to 45 kg/m 3 and most preferably of 30 to 40 kg/m 3 .
• the cell openness measured according to DIN EN ISO 4590 without correction, is between 30 and 90%.
• the rigid PUR foams produced by the process according to the invention are particularly suitable as intermediate layers for the manufacture of sandwich elements by the cold-forming process and for use as soft trim for cars, especially as inside roof linings, roof stiffening board and column trim.
• DABCO® NE-1060 from Air Products
• a silicone foam stabilizer (e) (Niax® Silicone SR 272 from GE Silicones),
• a cell opener (f) (Ortegol® 501 from Degussa Goldschmidt AG) and
• the component A and the component B were intimately mixed at 23° C. and filled into a paper-lined wooden box (volume 61), where they were foamed.
• the foams produced had the following properties: TABLE Comparative Comparative cream Example 1 Example 2 Example 3 Example 1 Example 2 Cream time [s] 18 18 20 22 23 Gel time [s] 42 43 42 48 42 Density 1 [kg/m 3 ] 28 24 32 30 29 Cell openness 2 [%] 98 97 97 79 98 Tensile strength 3 [kPa] 238 236 246 281 176 Elongation at break 3 [%] 28 27 19 25 14 1 according to DIN 53420, 2 according to DIN EN IS 4590 (uncorrected), 3 according to DIN 53430
• the foams according to Examples 1 to 3 had good formability.
• the formulation of Example 2 when applied to a double conveyor belt, produced boards of wall thickness 13.5 mm which, after removal of the facings, could be processed to inside roof linings by the cold-forming process without the foam breaking.
• the foam had a density of 38 kg/m 3 , a cell openness of 41%, a tensile strength of 400 kPa and an elongation at break of 22%.
• Foams produced from the formulation of Comparative Example 1 did not possess a sufficient cell openness for the manufacture of rigid PU foam boards that could be processed by the cold-forming process.
• Foams produced from the formulation of Comparative Example 2 did not possess adequate elongation and forming properties for the manufacture of inside roof linings by the cold-forming process.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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• 2004
  • 2004-12-24 DE DE102004062540A patent/DE102004062540A1/de not_active Withdrawn
• 2005
  • 2005-12-13 PL PL05027146T patent/PL1674493T3/pl unknown
  • 2005-12-13 AT AT05027146T patent/ATE464337T1/de not_active IP Right Cessation
  • 2005-12-13 EP EP05027146A patent/EP1674493B1/de not_active Expired - Lifetime
  • 2005-12-13 ES ES05027146T patent/ES2341345T3/es not_active Expired - Lifetime
  • 2005-12-13 DE DE502005009405T patent/DE502005009405D1/de not_active Expired - Lifetime
  • 2005-12-19 US US11/305,956 patent/US20060142407A1/en not_active Abandoned
  • 2005-12-21 CA CA2531250A patent/CA2531250C/en not_active Expired - Fee Related
  • 2005-12-22 JP JP2005369613A patent/JP5027412B2/ja not_active Expired - Fee Related

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